Nitrochlor derivatives of open-chain hydrocarbons and process of making same



Patented Dec, 9, H924.

warren-stares intact? earanr @FFEIQE.

ELIAS BIELOUSS, or wasnrneron, msrnrcr or COLUMBIA, Assrenoa T0 HENRY A.

GARDNER, or WASHINGTON, nrs'rnrcr or COLUMBIA.

NITROCHLOB. DERIVATIVES or ornn-cn'arn HYDBOCAR-BONS AND raoonss or '1i E.AKI1\TG SAME. r

No Drawing.

Making Same, of which the following is specification.

This invention relates to certain novel products derivable from liquid or liquefiable hydrocarbons of the open-chain type by subjecting them or mixtures thereof to the successive steps of chlorination and nitra- -tion. With proper control of the process it is possible to obtain either solid or liquid ,nitro-chlor derivatives, both of these forms being usually produced simultaneously but in varying proportions according to the operating conditions. Both types of products possess properties indicating their applicability to numerous uses in the arts,1,for example as components of varnishes and of plastic .moldmgcompositlons, and the, like.

Only the lower'I-nembers of. the halogennitro-open-chain hydrocarbonshave been heretofore known; and the principal methods for their preparation have involved the breaking down of hydrocarbon complexes, usually-of the closed-chain"type.- A familiar example ofthis' is the preparation of chlor-- picrin, CCI NO which can be madeeither by the nitration of chloral or by the chlor- -ination of picric acid. .Nitro-chlor derivatives of aromatic hydrocarbons are on the. p

. tionate yield of the solid and 11 md nitrochlor derivatives will vary consi erably'accontrary well known.

, I have found that whereas the 'paraflins themselves are exceptionally indifferent to nitrating agents, they acquire a pronounced reactivity toward such agents by theprevious introduction of ehlorin into the chain. My novel process consists essentially therefore in subjecting to-anitrating process the chlorine derivatives of liquid'or liquefiable open-chain hydrocarbons.

The chlorination may be carried out in any of-the well known, ways, either with or without the addition of 1a catalyst,'and need not thereforebe' further described. -It has been observed, however, contrary to expectation, that whereas'hydrocarbonoils contain ing a limited chlorin' content (say up to- 360 parts of sulfuric aci Application filed July 80, 1921. Serial No. 488,697.

20-25% chlorin based on the weight of the original oil) tend to yield a large proportion of solid resinous 'nitro-chlor derivatives, the

oils of decidedly higher chlorination (say being readily-miscible with nitrocellulose f olutlons, and maybe compounded with nitrocellulose in the preparation of plastics.

either with or without nitrocellulose, yield continuous varnish films on evaporation.

The nitration may be carried out invarious ways, usually involving the use of sulfuric and nitric acids, or .of sulfuric acid and a nitrate. 'For'example the chlorinated hydrocarbons may be, introduced directly into the nitrating bath (sulfuric and nitric acids) or the chlorinatedhydrocarbons may The solutionsof the nitro-chlor derivatives,

be first mixed with sulfuric acid and thenitric acid-added to the mixture; or the chlorinated hydrocarbon may be' mixed with .sodium nitrateand the mixture introduced into the. sulfuric acid ;bath.-. The proporcording' to the-specific.v operating method chosen. a v

' Example I.

17% of chlorln by'weight of the oil had been absorbed. 100 parts by weight of this chlorinated oil were added in small portions with stirring toa nitratin bath containing: (97%) parts of nitric acid The temperature'was not permitted to rise above55 C. After standing a few hours the nitro-chlor derivative' was parted from the residual acid, and

' and dried at room temperature;

' the solid resin separated from the liquid by pressure filtration.

Em a 12.

thorou 100 parts of the abovechlorinated oil were mixed with 360' parts of sulfuric acid (97%),

and 65' parts of nitric acid (70%) were added to the mixturein' small successive per-+ tions. i After treating the reaction mixture as above '50 parts of a dark yellow resin were recovered.

Ewample LU. 100 parts of a chlorinated oil containing '18%*of'ch1orin were mixed with 160 parts of sulfuric acid- (97%) i and 65 I partsot nitric acid (70%) were added insmall successive portions to the mixture. The product Was treated as above and d6 parts of a brown resin were recovered.

Example I V.

"100 parts of the above, chlorinated oil ere rnixedvvith 60 parts of sodium nitrate,

and 80 parts ofisulfuric, acid were added to the mixture in small portions; About 25 i j parts of a brown resin were recovered.

The melting point of the solid nitro-chlor derivatives prepared as above'ranged 'from' WP-108 0. Their average nitrogen cone tent was approximately 3.4%.,

The liquid products are also principally; 'nitroechlor derivatives, and apparently some prise hoth nitr0-chlor derivativesof lower nitrogen content, andnitro-chlor derivatives "of the lower-boiling components of the original oil.

I claim: Process: of making nitro chlor derivatives jecting a paraffin type mineral oil distillate of a specific gravity of not lessthan 0 .882 successively to chlorination and nitration.

In testimony whereof, T affixmy signature.

' Y ELIAS BTELUUSS.

, fov oen-chain hydrocarbons co prisi 1 

